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Title: Combining STM, RAIRS and TPD to Decipher the Dispersion and Interactions Between Active Sites in RhCu Single-Atom Alloys

Abstract

Single-atom alloys are a new class of heterogeneous catalyst in which trace amounts of metal dopants exist as individual, isolated sites in a host metal. In this study, we examine RhCu, a new single-atom alloy with a combination of scanning tunneling microscopy, reflectance absorbance infrared spectroscopy, and temperature programed desorption to understand the atomic structure of the alloy and correlate this with the behavior of CO, a common probe molecule. Here, we find that Rh alloys into Cu(111) preferentially from step edges. As such, step density plays an important role in the vibrational structure of CO on isolated Rh sites. We observe that atomically dispersed Rh sites can be close enough together to have dipole-dipole coupling interactions. Together, this combined experimental approach enables us to understand the alloying mechanism of Rh with Cu and yields important signatures of the atomic sites that are useful in benchmarking CO vibrational data.

Authors:
 [1];  [1];  [1];  [1];  [2];  [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Tufts Univ., Medford, MA (United States)
  2. Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.; Imperial College, London (United Kingdom)
Publication Date:
Research Org.:
Tufts Univ., Medford, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1595290
Alternate Identifier(s):
OSTI ID: 1573523
Grant/Contract Number:  
SC0004738; FG02-10ER16170
Resource Type:
Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 12; Journal Issue: 2; Journal ID: ISSN 1867-3880
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Single-atom alloy; surface science; catalysis; microscopy; IR-spectroscopy

Citation Formats

Hannagan, Ryan T., Patel, Dipna A., Cramer, Laura A., Schilling, Alex C., Ryan, Paul T. P., Larson, Amanda M., Çınar, Volkan, Wang, Yicheng, Balema, Tedros A., and Sykes, E. Charles H. Combining STM, RAIRS and TPD to Decipher the Dispersion and Interactions Between Active Sites in RhCu Single-Atom Alloys. United States: N. p., 2019. Web. doi:10.1002/cctc.201901488.
Hannagan, Ryan T., Patel, Dipna A., Cramer, Laura A., Schilling, Alex C., Ryan, Paul T. P., Larson, Amanda M., Çınar, Volkan, Wang, Yicheng, Balema, Tedros A., & Sykes, E. Charles H. Combining STM, RAIRS and TPD to Decipher the Dispersion and Interactions Between Active Sites in RhCu Single-Atom Alloys. United States. doi:10.1002/cctc.201901488.
Hannagan, Ryan T., Patel, Dipna A., Cramer, Laura A., Schilling, Alex C., Ryan, Paul T. P., Larson, Amanda M., Çınar, Volkan, Wang, Yicheng, Balema, Tedros A., and Sykes, E. Charles H. Tue . "Combining STM, RAIRS and TPD to Decipher the Dispersion and Interactions Between Active Sites in RhCu Single-Atom Alloys". United States. doi:10.1002/cctc.201901488.
@article{osti_1595290,
title = {Combining STM, RAIRS and TPD to Decipher the Dispersion and Interactions Between Active Sites in RhCu Single-Atom Alloys},
author = {Hannagan, Ryan T. and Patel, Dipna A. and Cramer, Laura A. and Schilling, Alex C. and Ryan, Paul T. P. and Larson, Amanda M. and Çınar, Volkan and Wang, Yicheng and Balema, Tedros A. and Sykes, E. Charles H.},
abstractNote = {Single-atom alloys are a new class of heterogeneous catalyst in which trace amounts of metal dopants exist as individual, isolated sites in a host metal. In this study, we examine RhCu, a new single-atom alloy with a combination of scanning tunneling microscopy, reflectance absorbance infrared spectroscopy, and temperature programed desorption to understand the atomic structure of the alloy and correlate this with the behavior of CO, a common probe molecule. Here, we find that Rh alloys into Cu(111) preferentially from step edges. As such, step density plays an important role in the vibrational structure of CO on isolated Rh sites. We observe that atomically dispersed Rh sites can be close enough together to have dipole-dipole coupling interactions. Together, this combined experimental approach enables us to understand the alloying mechanism of Rh with Cu and yields important signatures of the atomic sites that are useful in benchmarking CO vibrational data.},
doi = {10.1002/cctc.201901488},
journal = {ChemCatChem},
number = 2,
volume = 12,
place = {United States},
year = {2019},
month = {9}
}

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